ph neutral Cleaning Agents Market Expectation & Field Performance

Transcription

1 ph neutral Cleaning Agents Market Expectation & Field Performance Umut Tosun, Jigar Patel, Kalyan Nukula, Fernando Gazcon ZESTRON Americas Manassas, VA Abstract With regard to precision cleaning applications within electronics manufacturing, ph neutral product development was a major breakthrough in recent years. The impetus for this development resulted from changes with regard to solder paste formulations and resulting assembly processes. The greater use of lead-free solder paste and the required higher reflow profiles have resulted in even more difficult to remove burnt-in flux residues. Coupled with increases in component density, larger component packages, higher lead counts, finer lead spacing, and lower standoff distances, effective cleaning is greatly challenged. The aqueous alkaline based cleaning agents can effectively remove these flux residues, however, the process often requires an increase in wash temperature and exposure time, chemical concentration, and mechanical energy. Although an efficient and effective cleaning process can be developed, oftentimes, the required operating parameters present a new set of challenges with regard to material compatibility. Since their introduction, the newly developed ph neutral formulations have proven to be capable not only of removing these difficult post reflow residues from complex board geometries, but do so without affecting material compatibility of sensitive components. Additionally, they perform at low concentration levels. This study reviews the performance of ph neutral cleaning agents as compared to alkaline cleaning agent alternatives and includes field data demonstrating their effectiveness with regard to material compatibility and cleaning performance. Introduction As engineered aqueous based cleaning agents are developed, they tend to be alkaline with ph values ranging from 8 to 14 for this is required in order to solubilize the burnt-in flux residues found on board surfaces. However, components are being developed with an increasing amount of sensitive materials and these can be adversely affected by alkaline cleaning agents. One way to address the material compatibility issues with alkaline cleaning agents is to add inhibitor packages, commonly referred to as corrosion inhibitors, to the cleaning agent formulation. Although these can minimize if not eliminate the detrimental impact to sensitive materials, inhibitor type and quantity is critical and must be properly balanced with the cleaner operating parameters in order to achieve effective results. An alternative solution is the use of ph neutral cleaning agents. These have the advantage of requiring small amounts of inhibitors in order to maintain the integrity of the sensitive material surfaces while retaining the cleaning effectiveness of the alkaline cleaning agents. ph neutral cleaning agents were introduced to the market in early 2010 with the promise of offering excellent material compatibility and cleaning effectiveness. They also offered environmental advantages such as the possibility of eliminating waste water neutralization processes as well as the option for a closed loop rinse water cycle. Since their introduction, this has proven to be the case. At SMTA International 2010, a study titled Benchmark Study: ph neutral vs. Alkaline Cleaning Agents was presented [1]. This study compared and documented the material compatibility and cleaning effectiveness of an alkaline cleaning agent with that of a ph neutral cleaning agent. An excerpt of this study is included as background information with regard to the key differences between ph neutral and alkaline cleaning agents. The complete study details a comparative analysis of the results of short and long term effects of ph neutral and alkaline cleaning agents on sensitive materials such as anodized, alodine and iridite coatings, electroless nickel plating as well as aluminum and copper. It also compares the cleaning effectiveness of each on the substrate surface and undercomponent utilizing spray-in-air inline cleaning equipment. Based on the results of this study, ph neutral cleaning agents held the promise of offering superior material compatibility, comparable if not improved cleaning performance and lower concentrations as compared to alkaline alternatives for cleaning No Clean, RMA and OA flux residues. This paper presents three customer case studies whereby the specific customer explored the option of employing a ph neutral cleaning agent due to issues with alkaline cleaning agents and/or DI-water with their cleaning processes.

2 Background (Excerpt from Benchmark Study: ph Neutral vs. Alkaline Cleaning Agents [1]) With the emergence of ph neutral defluxing technologies in early 2010, ph neutral formulations promised to set a new standard for material compatibility, while proving valuable to those who worked toward environmentally sound processes. As a result, potential users are very interested in assessing the differences between alkaline cleaning agents and the newer ph neutral products, with regard to both, cleaning performance and material compatibility. One area of particular interest is the cleaning agent impact on sensitive metals. Material compatibility issues between sensitive metals and cleaning solution arise when corrosion, i.e. the electrochemical deterioration of a metal due to the reaction with its environment, takes place. To prevent corrosion caused by the very cleaning solution that is meant to safeguard the assembly from corroding in-field and potentially fail, inhibitors come into play. In general, corrosion inhibitors are chemicals that form coordinative chemical bonds with metallic surfaces (adsorption), thereby developing a thin protective layer. They are normally distributed through a solution or by dispersion. Inhibitors slow corrosion processes by either increasing the anodic or cathodic polarization behavior, by reducing the movement or diffusion of ions to the metallic surface or by increasing the electrical resistance of the metal s surface. Corrosion inhibitors can be classified as either inorganic or organic, with the latter being more prevalent due to solubility advantages, performance, and fewer environmental concerns. Examples of typical corrosion inhibitors are silicates, borates, alkanolamines, naphthalenesulfonic acid, triazoles, carboxylic acids, molybdates, polyols, and phosphate [2]. If the respective cleaning media does not work as intended, several types of corrosion can commonly occur on electronic assemblies, such as gas phase, uniform, pitting, electrolytic metal migration, and galvanic [3]. Fortunately, this has been an area of much research and electronics manufacturers today have a variety of cleaning choices to prevent such issues with the newer and more effective aqueous alkaline chemistries strongly preferred over solvents or traditional surfactants. Recently, however, the choices of aqueous products available for defluxing have expanded significantly with the introduction of ph neutral formulations. For aqueous solutions to do a superior job without affecting sensitive metal substrates, i.e. corrosion control, manufacturers have to add inhibitors. Studies have shown that choosing the correct type and amount of inhibition chemistry is critically important. Otherwise, the inhibitors themselves can present several problems in the SMT production process. First, the solubility of certain inhibitors in chemistry concentrate is sometimes low and only a small percentage of the inhibitor can be added to the cleaning product formulation. Therefore, to achieve proper protection of sensitive metals using such problematic inhibitors, a higher recommended operating concentration is often required in the wash tank, which leads to unnecessary chemistry consumption. On the other hand, lowering the concentration leads to a lower amount of inhibitor available to protect sensitive metals. Second, these organic additives can have detrimental effects on the cleaning process as they also interact with any residue as well as the environment and inhibit the dissolution of such residue into the cleaning fluid. Finally and most importantly, certain inappropriate inhibitors are tightly bound to the metal surface and are more difficult or impossible to rinse from the substrate s surface and under components, where they linger insidiously, causing a host of problems over time. This contamination can adversely increase the electrical resistance of the contaminated areas, leading to conformal coating issues and causing unpredictable failures, thereby threatening the long-term reliability of the assembly. The type and amount of inhibitors selected is also a function of the ph conditions in the process. Some inhibitors that work well at a certain ph will not function as well or at all if the ph is outside of this range. Therefore, ph neutral cleaning agents offer distinct advantages and require very small amounts of inhibitors. At this ph range (7 +/- 0.5), a unique and customized set of corrosion inhibitors is very effective, thereby solving the problems mentioned above. Due to their lower surface tension (less than 30 mn/m vs. 72 mn/m for water), ph neutral solutions can penetrate the tiny spaces in and around components, do their job of removing contamination even at low concentrations and can be easily rinsed and dried [4]. Furthermore, ph neutral cleaners are more environmentally friendly and eliminate waste water neutralization processes. Most importantly, however, using ph neutral agents has been shown to eliminate material compatibility concerns in cases where alkaline agents have failed, thereby offering users a solution that previously did not exist. Case Study Review Customer A: Company A is a global OEM designing and producing electronic assemblies for numerous applications within the military, aerospace, automotive, industrial, and medical industries. A new customer was acquired and the plant in question was tasked with manufacturing the newly designed PCBs.

3 Within their current SMT process, this plant used an aqueous based inline spray-in-air cleaning process and an alkaline cleaning agent. Although this process produced satisfactory results, material compatibility issues arose with one particular substrate that was manufactured with lead-free solder paste and liquid flux. This PCB was double-sided and populated with capacitors, microprocessors and various size resistors and connectors. Additionally, the substrate included pluggable press fit cages or shields with a nickel silver coating. Reference Figures 1 and 2. Figure 1 - PCB Side 1 Figure 2 PCB Side 2 It should be noted that it was critical to maintain the integrity of the shield material throughout the manufacturing process. As doubled-sided substrates, they were passed through reflow and wave consecutively, and then cleaned employing the current cleaning process. As this system had been satisfactorily used for many years, plant personnel planned to use this system to meet the cleaning challenges of the new substrate. Utilizing the alkaline cleaning agent at 15% concentration and a belt speed of 0.5 ft/min, two passes through the cleaner were required due to the resulting burnt-in fluxes from multiple heat cycles. However, even as they were able to clean the substrates, the surface of the shields became degraded. Thus, a new cleaning process was required. Furthermore, as the initial cleaning trials progressed, a second material compatibility issue developed as a result of an additional assembly step. A third party sourced subassembly with a polyurethane conformal coating had to be added to the main substrate, prior to the cleaning process. As the customer attempted multiple wash cycles to achieve the desired cleanliness level, the added wash time also affected the conformal coating causing peeling. The customer partnered with the company and developed a two part Design of Experiment (DOE) to resolve both material compatibility issues. Part 1: Utilizing their current cleaning system, identify an alternate aqueous based cleaning agent and utilizing the customers current cleaner, develop the process parameters to achieve the desired cleaning results without degrading shield coating. Part 2: Utilizing the cleaning process parameters developed in Part 1, assess the compatibility of the selected cleaning agent with conformal coating materials recommending an optimum solution. Part 1: Design of Experiment The DOE was based on utilizing the current inline cleaning system. Based on the material compatibility issues identified, a ph neutral cleaning agent was selected for the initial trials. Preliminary cleaning trials were conducted in the customer plant utilizing the ph neutral cleaning agent. Optimum parameters were developed as detailed in Table 1.

4 Table 1 Preliminary Cleaning Trial Parameters Wash Stage Equipment Inline spray-in-air cleaner Cleaning Agent: ph neutral micro phase Concentration: 20% Conveyor Belt Speed 0.5 ft/min Wash Pressure (Top/Bottom) 65 PSI / 65 PSI Wash Temperature 145 F / C Rinsing Stage Rinsing Agent DI-water Rinse Temperature 101 F / C Drying Stage Drying Method Hot Circulated Air, 102 F-111 F / C C Utilizing these conditions, three production boards were cleaned and sent to the company technical center in Manassas, VA, for a cleanliness assessment. The boards were analyzed through visual inspection and ion chromatography. The inspected boards were returned to the customer for functional tests. Part 1: Visual Inspection Results Visual inspection was conducted following IPC-A-610E. All of the boards were found to be fully cleaned. Reference Figures 3 6. Figure 3 Bottom Figure 4 Bottom Figure 5 Top Figure 6 Top Shield surface was unaffected. Reference Figures 7 and 8.

5 Figure 7 Top Figure 8 Top As indicated through visual inspection, the substrate top and bottom surfaces were fully cleaned and the surfaces of the shields were left unaffected, therefore found to be fully compatible with the ph neutral cleaning agent. Part 1: Ion Chromatography Results Ion chromatography was conducted on all three boards per IPC-TM-650, Method Results are detailed in Table 2. Table 2 Anion Species Always Tested For (µg/in 2 ) Maximum Ionic Species Contamination Board 1 Board 2 Board 3 Limits Fluoride (F - ) Acetate (C 2H 3O - 2 ) ND ND Formate (CHO - 2 ) 3 ND ND Chloride (Cl - ) Nitrite (NO - 2 ) Bromide (Br - ) Nitrate (NO - 3 ) Phosphate (PO 2-4 ) Sulfate (SO 2-4 ) WOA (Weak Organic Acid) Cation Species Always Tested For (µg/in 2 ) Lithium (Li + ) 3 ND ND ND Sodium (Na + ) Ammonium (NH + 4 ) Potassium (K + ) Magnesium (Mg 2+ ) 1 ND ND ND Calcium (Ca 2+ ) 1 ND ND ND ND Not Detected 0 Blank value is higher than sample value All boards passed further validating that the cleanliness level desired was achieved with the ph neutral cleaning process. The boards were returned to the customer and found to be fully functional. Part 2: Design of Experiment Following Part 1 trials and cleanliness assessments, the customer was satisfied that the ph neutral cleaning process could result in achieving the desired cleanliness levels for the new substrates and is fully compatible with all materials used. Within Part 2 of the DOE, they assessed the compatibility of the optimized cleaning process with conformal coating materials. Three coating types were compared for the initial compatibility analysis. These were parylene, acrylic and polyurethane. Based on internal tests conducted at the company R&D Center, parylene coating was found to be most compatible with the ph neutral cleaning agent. Thus, the next step was to coat substrates with the parylene and evaluate compatibility within the customers cleaning process utilizing the operating conditions identified in Part 1.

6 In this case, the substrate used was an unpopulated company test vehicle. Reference Figure 9. Figure 9 Three test boards were sent to the coating supplier for the parylene application. Each board was coated with a 33 µm layer of parylene-based conformal coating material. The boards were returned to the company technical center where they were subjected to a cleaning process utilizing an inline cleaner, similar to the one used by the customer, and operated with the same parameters as defined in Part 1. However, in this case, the boards were passed through the cleaner twice. Following the cleaning process, they were visually inspected under high magnification following the IPC-A-610E. Part 2: Parylene Coating Visual Inspection Results Based on the visual inspection results of the coated test vehicle following the first and second pass through the inline cleaner, the coating was found to be intact. Reference Figures Figure 10 - Before Figure 11 - After (1 pass)

7 Figure 12 - Before Figure 13 - After (2 pass) Conclusions The ph neutral cleaning process identified through the Part 1 cleaning trials resulted in: Fully cleaned the double-sided substrates assembled with lead-free solder paste and flux utilizing the customer s current spray-in-air inline cleaner, and optimized for the ph neutral cleaning agent Exhibited excellent material compatibility with the nickel silver shield coating Exhibited excellent material compatibility with the parylene conformal coating Case Study Review Customer B Customer B is a value-added electronic manufacturing service provider to some of the world s leading OEMs. They specialize in PCBA and full product assembly, plastic molding, precision metal stamping, fabrication and finishing, and engineering services with products ranging from simple consumer devices to complex, high end commercial and industrial electro-mechanical products. They had an opportunity to qualify a new manufacturing process for a high reliability electronic assembly for a medical application. The SMT process utilized No Clean solder paste and flux that required cleaning for which the customer planned to utilize an aqueous based inline cleaning process. In addition to sensitive materials on the substrate surface, the new process included the use of anodized aluminum carriers to hold the substrates as they are conveyed through the cleaner. Thus, a cleaning agent with excellent material compatibility was required. The customer collaborated with the company to develop the cleaning process for their qualification. Based on the process and material compatibility requirements, a ph neutral aqueous based cleaning agent was selected. Design of Experiment The customer substrate was designed as a panel and each panel included 18 boards. Uncleaned substrates, double-sided and populated, and pallets were provided to the company for the initial cleaning trials. In total, six (6) panels and twelve (12) boards were provided for the evaluation. Reference Table 3. A spray-in-air inline cleaner was selected for the cleaning process. Substrate Type Main Board Speculum Board Scrap Boards Table 3 Quantity 5 Panels 1 Panel 12 Boards

8 The Main and Speculum boards are part of the same assembly and the name is used for reference only. Cleanliness was assessed as follows: Visual inspection per IPC-610E Standard: before and after cleaning Ionic contamination analysis per IPC-TM-650 Ion chromatography analysis per IPC-TM-650; Method The boards and panels were utilized as detailed in Table 4. Table 4 Test # Parts Cleaned Quantity Pallet Used Post Cleaning Analysis 1 Scrap boards 6 Yes - Visual inspection (2) - Ionic contamination (4) 2 Scrap boards 6 No Visual inspection 3 Main Board Panel 1 No Ion chromatography Speculum Board Panel 1 No Ionic contamination Main Board Panel 1 Yes Customer B will conduct analysis 4 Main Board Panel 3 Yes Customer B will conduct analysis All panels were passed through the inline cleaner utilizing the anodized aluminum carriers. The carriers were inspected for surface integrity following the cleaning process. With regard to the cleaning process, initial screening trials confirmed that the ph neutral cleaning agent used at 10% concentration and 145 F wash temperature would be sufficient to clean the substrates. The optimized inline cleaner operating parameters are detailed in Table 5. Table 5 Wash Stage Equipment Inline cleaner Cleaning Agent Type ph neutral micro phase Cleaning Agent Concentration 10% Conveyor Belt Speed 1.5 ft/min Wash Temperature 145 F / 62.7 C Rinsing Stage Rinsing Agent DI-water Rinse Temperature 145 F / 62.7 C Drying Stage Drying Method Hot circulated air, 160 F (D1), 230 F (D2), 240 F (D3) Results: Visual Inspection Utilizing the inline cleaner with the operating parameters as detailed in Table 5, all boards and panels were cleaned in one pass. Reference Figures for before and after cleaning comparisons.

9 Figure 14 Before Cleaning Figure 15 After Cleaning Figure 16 Before Cleaning Figure 17 After Cleaning Figure 18 Before Cleaning Figure 19 After Cleaning Figure 20 Before Cleaning Figure 21 After Cleaning

10 Figure 22 Before Cleaning Figure 23 After Cleaning Figure 24 Before Cleaning Figure 25 After Cleaning Ionic Contamination Test Results For the ionic contamination test procedure, four (4) of the scrap boards were used. These were tested before and after the cleaning process. As expected, there is a significant difference in the results following the cleaning process. The Speculum board was also tested but only following the cleaning process. This board passed as well. Reference Table 6. Table 6 Test # Part Type Quantity Pass/Fail Limit Ionic Contamination Value 1 Scrap Boards (before cleaning) µg/in µg/in 2 2 Scrap Boards (after cleaning) µg/in µg/in 2 3 Speculum Board Panel (after cleaning) µg/in µg/in 2 Ion Chromatography Results One (1) panel was cleaned and used for ion chromatography analysis. The results are detailed in Table 7. Table 7 Anion Species Always Tested For (µg/in 2 ) Ionic Species Maximum Contamination Levels Panel Fluoride (F - ) Acetate (C 2H 3O - 2 ) 3 ND Formate (CHO - 2) 3 ND Chloride (Cl - ) Nitrite (NO - 2 ) Bromide (Br - ) Nitrate (NO - 3 ) Phosphate (PO 2-4 ) 3 ND

11 Sulfate (SO 2-4 ) WOA (Weak Organic Acid) 25 ND Cation Species Always Tested For (µg/in 2 ) Lithium (Li + ) 3 ND Sodium (Na + ) Ammonium (NH + 4 ) Potassium (K + ) Magnesium (Mg 2+ ) Calcium (Ca 2+ ) ND Not Detected 0 Blank value is higher than sample value As detailed in Table 7, the board passed the ion chromatography test as the ion species were below the maximum recommended contamination level. Conclusion The ph neutral cleaning agent: Successfully cleaned all substrates Exhibited excellent material compatibility with all substrate components as well as the anodized aluminum carriers Required 10% concentration 1.5 ft/min belt speed and 145 F wash temperature minimizing operating costs Case Study Review Customer C Customer C is an OEM designing and manufacturing high-reliability electronic control systems for the aerospace and energy industry. For one of their applications, substrates were manufactured with water soluble solder paste and flux and cleaned using a DIwater inline cleaner. Through visual inspection analysis, they confirmed that residues were left untouched underneath the low standoff components potentially leading to reliability issues. They wanted to explore the option of utilizing a water based engineered cleaning agent in order to increase the cleanliness level for the given substrates and preferred to use a batch cleaner due to plant space constraints. However, if an aqueous based cleaning agent is used, it must be compatible with their component materials including anodized aluminum and olive drab cadmium. Also, given their geographic location, a closed loop rinse cycle is mandatory as rinse water cannot go directly to drain. In collaboration with the company, a DOE was developed to explore the option of a chemically assisted cleaning process. Due to their requirements for material compatibility and a closed loop rinse cycle, a ph neutral cleaning agent was selected. Design of Experiment The DOE was divided into two parts with the following objectives: Part 1: Utilizing populated company test vehicles, the ph neutral cleaning agent and a batch cleaner, assess and optimize the process operating parameters to achieve the desired cleanliness level on the surface as well as underneath the components as measured by visual and ion chromatography analyses. Compare these results to those achieved with the customer s DI-water cleaning system. Part 2: Utilizing the equipment and optimized process parameters from Part 1, and the customer s test boards, assess cleanliness level achieved as measured by visual and ion chromatography analyses. Additionally, assess the effect of the cleaning agent on the sensitive materials. Part 1: Methodology Since the customer requirement included cleaning under low standoff components, the company test vehicle was used. Eight (8) boards were populated with chip capacitors (0402, 0603, 0805, SOT-23, 1206, 1210, 1812, and 1825) at the customer facility using the selected water soluble paste and flux. Reference Figure 26.

12 Figure 26 Two (2) of these boards were cleaned at the customer site using their current DI-water cleaning process. These boards were returned to the company technical center for cleanliness assessment, one each for undercomponent and ion chromatography assessment. The remaining six (6) boards were also returned for cleaning trials using the ph neutral cleaning process and cleanliness assessment. Based on screening trials utilizing four (4) of the test boards, optimized operating parameters were defined and are detailed in Table 8. Two (2) additional boards were cleaned using these parameters and both were assessed for surface cleanliness. The components were removed from one (1) board to enable undercomponent cleanliness assessment and the other used for ion chromatography analysis. The optimized process parameters are detailed in Table 8. Table 8 Cleaning Process Cleaner Equipment Batch cleaner Cleaning Agent Type ph neutral micro phase Cleaning Agent Concentration 10% Cleaning Time 15 min. Cleaning Temperature 140 F / 60 C Rinse Rinsing Agent DI-water Rinse Temperature Room Temperature Number Rinses Required 5 each with a dwell time of 20 seconds Drying Drying Method Hot Circulated Air Drying Time / Temperature 15 min. / 150 F / 65.5 C Table 9 Visual Inspection Results DI-water Cleaned ph neutral Cleaned Surface Inspection White residues remained Fully cleaned Undercomponent Inspection Residues remained Fully cleaned Reference Figures for undercomponent cleanliness comparison:

13 White residue Figure 27 - Underneath 1825 Component After Cleaning using DI-water Figure 28 - Underneath 1825 Component After Cleaning using ph neutral White residue Figure 29 - Underneath 1812 Component After Cleaning using DI-water Figure 30 - Underneath 1812 Component After Cleaning using ph neutral Figure 31 - Underneath 0402 Component After Cleaning using DI-water Figure 32 - Underneath 0402 Component After Cleaning using ph neutral Figure 33 - Underneath 0603 Component After Cleaning using DI-water Figure 34 - Underneath 0603 Component After Cleaning using ph neutral Part 1: Ion Chromatography Results

14 Two (2) boards were used for ion chromatography analysis, one cleaned with DI-water and another with the ph neutral cleaning agent. Results are detailed in Table 10. Table 10 Anion Species Always Tested For (µg/in 2 ) Ionic Species Maximum DI-water Cleaned ph neutral Cleaned Contamination Limits Fluoride (F - ) Acetate (C 2H 3O - 2 ) Formate (CHO - 2 ) 3 ND ND Chloride (Cl - ) Nitrite (NO - 2 ) 3 ND ND Bromide (Br - ) Nitrate (NO - 3 ) Phosphate (PO 2-4 ) Sulfate (SO 2-4 ) WOA (Weak Organic Acid) 25 ND ND Cation Species Always Tested For (µg/in 2 ) Lithium (Li + ) Sodium (Na + ) Ammonium (NH + 4 ) Potassium (K + ) Magnesium (Mg 2+ ) Calcium (Ca 2+ ) ND Not Detected 0 Blank value is higher than sample value Both boards passed the ion chromatography test for the ion species were below allowable maximum contamination levels. However, the total ionic contamination present on board cleaned with the ph neutral cleaning agent was less than what was present on the DI-water cleaned board. Additionally, the undercomponent assessment of the DI-water cleaned board confirmed that untouched flux residue remained under several components providing the opportunity for field reliability issues under use. Reference Figures 27 and 29. Part 2: Methodology Having confirmed that low standoff components can be fully cleaned on the surface as well as underneath the components, the customer provided with five (5) test boards for process assessment. Reference Figure 35. Figure 35 Utilizing the same batch equipment and optimized parameters as used in Part 1, the boards were cleaned and assessed for cleanliness using visual and ion chromatography assessment. The customer boards are double-sided thereby increasing the cleaning challenge. Thus, it was determined to increase the wash temperature to 150 F, as compared to 140 F as used in the Part 1 trials. All other batch cleaner operating parameters remained the same. Part 2: Visual Inspection Results

15 All five (5) boards were cleaned using the optimized cleaning process. Surfaces were fully cleaned on all boards. Of the five (5) boards, one was used for ion chromatography analysis. Of the four (4) remaining boards, components were removed enabling undercomponent cleanliness assessment. Of the one hundred (100) components inspected, only four (4) components from two (2) boards had slight residue remaining while all others were fully cleaned underneath. Table 11 Cleaning Results Underneath Board # 101 Board # 102 Board # 103 Board # 104 C C C C C C C C R C C C C C C C C C C R C C C C C : Clean - : Uncleaned Reference Figures 36 to 43 for undercomponent post cleaning pictures. Part 2 Minor white residue in depth area Figure 36 - Underneath C30 Figure 37 - Underneath C82

16 Figure 38 - Underneath R50 Figure 39 - Underneath C108 Figure 40 - Underneath C249 Figure 41 - Underneath C227 Figure 42 - Underneath C200 Figure 43 - Underneath C152 Part 2: Ion Chromatography Results

17 Table 12 Anion Species Always Tested For (µg/in 2 ) Ionic Species Maximum Contamination Limits Board # 105 Fluoride (F - ) Acetate (C 2H 3O - 2 ) 3 ND Formate (CHO - 2 ) 3 ND Chloride (Cl - ) Nitrite (NO - 2 ) 3 ND Bromide (Br - ) Nitrate (NO - 3 ) Phosphate (PO 2-4 ) 3 ND Sulfate (SO 2-4 ) 3 ND WOA (Weak Organic Acid) 25 ND Cation Species Always Tested For (µg/in 2 ) Lithium (Li + ) 3 ND Sodium (Na + ) 3 0 Ammonium (NH + 4 ) 3 0 Potassium (K + ) 3 0 Magnesium (Mg 2+ ) 1 ND Calcium (Ca 2+ ) 1 ND ND Not Detected 0 Blank value is higher than sample value The sample board passed the ion chromatography test. The ion species were below allowable maximum contamination levels. Conclusions The ph neutral cleaning agent: Provided excellent cleaning results on the surface and underneath the components with an optimized batch cleaning system Exhibited excellent material compatibility with anodized aluminum and olive drab cadmium material Required 10% concentration 1.5 ft/min belt speed and 150 F wash temperature minimizing operating costs Overall Conclusions As reviewed in the background and introduction of this study, ph neutral cleaning agents held the promise of offering superior material compatibility and excellent cleaning results as compared to the inhibited alkaline cleaning agents currently available for various paste and flux residues. In this study, three case studies were presented, each with a different paste/flux vehicle and material compatibility constraints whereby a ph neutral process cleaning solution was identified as follows: Customer A: Situation: o Lead-free solder paste and flux system producing double-sided substrates o Currently using an alkaline cleaning agent in spray-in-air process o Material compatibility issues with nickel/silver plating and conformal coating Resolution: o ph neutral cleaning agent optimized within their current cleaning process at 20% concentration and 145 F wash temperature o Desired cleanliness level achieved; fully compatible with nickel/silver plating and conformal coating Customer B: Situation: o No Clean solder paste and flux system producing double-sided substrates o Required to qualify a cleaning process for the new substrate without degrading the anodized aluminum carriers Resolution: o ph neutral cleaning agent optimized for an inline cleaning process at 10% concentration and 145 F wash temperature o Qualified the new cleaning process o Desired cleanliness level achieved; fully compatible with substrate components and anodized aluminum carriers Customer C: Situation:

18 o Water soluble paste and flux system o Utilizing a DI-water inline cleaning process; residues remain under components o Substrate components included anodized aluminum and olive drab cadmium o Required alternate cleaning system with improved performance without degrading component surface materials; preferred batch cleaning process Resolution: o ph neutral cleaning agent optimized for a batch cleaning process at 10% concentration and 150 F wash temperature o Desired cleanliness level achieved; able to meet their environmental requirement for closed loop rinse cycle. In summary, ph neutral cleaning agents can in fact meet the stringent cleaning requirements expected, even with burnt-in flux residues from multiple heat cycles, while exhibiting excellent material compatibility and with lower wash concentrations as compared to alkaline alternatives. Additionally, it is environmentally friendly eliminating the need for waste water neutralization. References [1] Dr. Harald Wack, Benchmark Study: ph-neutral vs. Alkaline Cleaning Agents, Proceedings of SMTA International, October 2010 [2] Michael and Irene Ash, Handbook of Corrosion Inhibitors, Synapse Information Resources, Inc., [3] Cleanliness and Corrosion Mitigation, ACI Technologies, Inc., Circuits Assembly, April [4] Dr. Harald Wack, Umut Tosun, Dr. Joachim Becht, Dr. Helmut Schweigart, Why Switch from Pure DI-Water to Chemistry? SMTA International 2009.

19 ph neutral Cleaning Agents Market Expectation and Field Performance Umut Tosun, M.S.Chem.Eng. Application Technology Manager ZESTRON Americas

20 Outline Introduction Background Case Studies Customer A Customer B Customer C Conclusion

21 Introduction Industry Trends Leaded to lead-free Increase in component density Smaller component packages Higher lead counts Finer lead spacing Lower standoff heights Trend

22 Introduction Aqueous based cleaning agents Alkaline based ph values ranging from 8 to 14 Required to solubilize burnt-in flux residues Modern components are designed with sensitive materials Can be adversely affected by alkaline agents

23 Corrosion occurs Introduction Due to material compatibility between sensitive metals and cleaning solution Corrosion prevention Addition of inhibitors to cleaning solution

24 Introduction Inhibition chemistry selection is critical Only a small percentage can be added to the cleaning solution formulation due to low solubility in concentrate Detrimental effects as they interact with any residue Inappropriate inhibitors are tightly bound to metal surface and more difficult to rinse from substrate surface and under components

25 Introduction ph neutral cleaning agents Alternative to alkaline cleaning agents Require small amount of inhibitors to maintain integrity of sensitive material surfaces Result in similar or improved cleaning effectiveness Eliminates waste water neutralization process

26 Outline Introduction Background Case Studies Customer A Customer B Customer C Conclusion

27 Background ph neutral introduced in early 2010 Previous research indicated Superior material compatibility Improved cleaning performance at lower concentrations Effectively clean No Clean, RMA and OA flux residues

28 Background ph neutral cleaning agent advantages Require very small amount of inhibitors Lower surface tension allows it to penetrate tiny spaces in and around components Remove contamination at low concentrations Easily rinsed and dried Eliminate material compatibility concerns where alkaline agents fail

29 Background Three customer case studies exploring ph neutral options due to issues with alkaline cleaning agents and/or DI-water within their cleaning processes

30 Outline Introduction Background Case Studies Customer A Customer B Customer C Conclusion

31 Type Customer A Global OEM designing and producing electronic assemblies for military, aerospace, automotive, industrial, and medical industries Issue Material compatibility issues arose with substrate surface and components

32 Substrate details Customer A Double-sided Lead-free solder paste and liquid flux Polyurethane conformal coated sub assemblies

33 Customer A PCB Side 1 PCB Side 2

34 Customer A Current cleaning process Spray-in-air inline cleaner Alkaline cleaning agent at 15% concentration 0.5 ft/min belt speed Two passes were required to fully clean due to burnt-in fluxes

35 Customer A Multiple passes resulted in material compatibility issues Nickel/Silver plated shield surface was degraded Conformal coating peeled A new cleaning process was required

36 Customer A Two part Design of Experiment (DOE) developed: Part 1 Utilizing current cleaning system, identify alternate aqueous based cleaning agent Develop process parameters without degrading shield coating Part 2 Assess compatibility of selected cleaning agent with conformal coating material

37 Customer A Part 1: ph neutral cleaning agent was selected Optimum parameters were developed Boards were cleaned and sent for cleanliness assessment

38 Optimum parameters: Customer A Wash Stage Equipment Spray-in-air inline Cleaning Agent ph neutral Concentration 20% Conveyor Belt Speed 0.5 ft/min Wash Pressure (Top/Bottom) 65 PSI / 65 PSI Wash Temperature 145 F / C Rinsing Stage Rinsing Agent DI-Water Rinse Temperature 101 F / C Drying Stage Drying Method Hot Circulated Air Drying Temperature 102 F 111 F / C C

39 Customer A Results Part 1: Visual Inspection Boards

40 Customer A Results Part 1: Visual Inspection Boards

41 Customer A Results Part 1: Visual Inspection Shields

42 Customer A Results Part 1: Ion Chromatography Anion Species Always Tested For (µg/in 2 ) Ionic Species Maximum Contamination Limits Board 1 Board 2 Board 3 Fluoride (F - ) Acetate (C 2 H 3 O 2- ) ND ND Formate (CHO 2- ) 3 ND ND Chloride (Cl - ) Nitrite (NO 2- ) Bromide (Br - ) Nitrate (NO 3- ) Phosphate (PO 2-4 ) Sulfate (SO 2-4 ) WOA (Weak Organic Acid) ND: Not Detected 0: Blank Value is higher than sample value

43 Customer A Results Part 1: Ion Chromatography Cation Species Always Tested For (µg/in 2 ) Lithium (Li + ) 3 ND ND ND Sodium (Na + ) Ammonium (NH 4+ ) Potassium (K + ) Magnesium (Mg 2+ ) 1 ND ND ND Calcium (Ca 2+ ) 1 ND ND ND ND: Not Detected 0: Blank Value is higher than sample value

44 Part 2: Customer A Assess compatibility of optimized cleaning process with conformal coating materials Three coating types Parylene Acrylic Polyurethane Parylene was found most compatible with ph neutral cleaning agent

45 Customer A Three test boards were sent to coating supplier Each board coated with 33µm layer All boards were Cleaned using optimum parameters identified in Part 1 Passed through the cleaner twice Visually inspected under high magnification

46 Customer A Results Part 2: Visual Inspection Before After (1 Pass)

47 Customer A Results Part 2: Visual Inspection Before After (2nd Pass)

48 Customer A Conclusions ph neutral cleaning process Achieved desired cleaning results Exhibited excellent material compatibility with nickel silver shield coating Exhibited excellent material compatibility with parylene conformal coating

49 Outline Introduction Background Case Studies Customer A Customer B Customer C Conclusion

50 Type Customer B Value-added EMS provider Products ranging from simple consumer devices to complex, high-end commercial and industrial electro-mechanical products Issue Qualify new manufacturing process for highreliability electronic assembly medical application

51 Customer B Current SMT process utilizes No Clean solder paste and flux with aqueous based inline cleaner New process Sensitive materials on substrate surface Anodized aluminum carriers to hold substrates Required cleaning agent with excellent material compatibility

52 Customer B Customer substrate designed as a panel Each panel includes 18 boards Provided boards and pallets for initial cleaning trials Substrate Type Main Board Panel Scrap Boards Quantity 6 Panels 12 Boards

53 Customer B Spray-in-air inline cleaning process selected Cleanliness assessed through Visual inspection Ionic contamination analysis Ion chromatography

54 Customer B Test # Parts Cleaned Quantity Pallet Used Post Cleaning Analysis 1 Scrap Boards 6 Yes Visual Inspection (2) Ionic Contamination (4) 2 Scrap Boards 6 No Visual Inspection 3 Main Board Panel 2 No Ion Chromatography Main Board Panel 1 Yes Customer to conduct 4 Main Board Panel 3 Yes Customer to conduct Passed through inline cleaner utilizing anodized aluminum carriers

55 Customer B ph neutral cleaning agent was selected Optimum parameters were developed Wash Stage Equipment Cleaning Agent Spray-in-air inline ph neutral Concentration 10% Conveyor Belt Speed Wash Temperature 1.5 ft/min 145 F / 62.7 C Rinsing Stage Rinsing Agent Rinse Temperature DI-water 145 F / 62.7 C Drying Stage Drying Method Drying Temperature Hot Circulated Air 160 F (D1), 230 F (D2), 240 F (D3)

56 Customer B Results Visual Inspection Before Cleaning After Cleaning

57 Customer B Results Visual Inspection Before Cleaning After Cleaning

58 Customer B Results Visual Inspection Before Cleaning After Cleaning

59 Customer B Results Visual Inspection Before Cleaning After Cleaning

60 Customer B Results Visual Inspection Before Cleaning After Cleaning

61 Customer B Results Visual Inspection Before Cleaning After Cleaning

62 Customer B Results Ionic Contamination Results Test # Part Type Quantity Pass/Fail Limit Scrap Boards (before cleaning) Scrap Boards (after cleaning) Main Board Panel (after cleaning) Ionic Contamination Value µg/in µg/in µg/in µg/in µg/in µg/in 2

63 Customer B Results Ion Chromatography Anion Species Always Tested For (µg/in 2 ) Ionic Species Maximum Contamination Levels Panel Fluoride (F - ) Acetate (C 2 H 3 O - 2 ) 3 ND Formate (CHO - 2) 3 ND Chloride (Cl - ) Nitrite (NO 2- ) Bromide (Br - ) Nitrate (NO 3- ) Phosphate (PO 2-4 ) 3 ND Sulfate (SO 2-4 ) WOA (Weak Organic Acid) 25 ND ND: Not Detected 0: Blank Value is higher than sample value

64 Customer B Results Ion Chromatography Cation Species Always Tested For (µg/in 2 ) Lithium (Li + ) 3 ND Sodium (Na + ) Ammonium (NH 4+ ) Potassium (K + ) Magnesium (Mg 2+ ) Calcium (Ca 2+ ) ND: Not Detected 0: Blank Value is higher than sample value

65 Customer B Conclusions ph neutral cleaning process resulted in Successful cleaning of all substrates Excellent material compatibility with all components as well as anodized aluminum carriers Optimum parameters Concentration: 10% Belt Speed: 1.5 ft/min Wash temperature: 145 F / 62.7 C

66 Outline Introduction Background Case Studies Customer A Customer B Customer C Conclusion

67 Type Customer C OEM that designs and manufacturers high-reliability electronic control systems for aerospace and energy industry Utilizes OA solder paste, DI-water and spray-in-air inline cleaner Issue Residues remaining underneath low standoff components

68 Customer C Objective Seeking water-based engineered cleaning agent: Achieve desired cleanliness level Utilize batch cleaner Excellent material compatibility with anodized aluminum and olive drab cadmium components Closed loop rinse cycle

69 Customer C ph neutral cleaning agent was selected DOE was divided into two parts Part 1 Using cleaning company s test vehicles, determine optimum process parameters as confirmed by visual inspection and ion chromatography Compare results to current DI-water cleaning process

70 DOE Part 2 Customer C Utilize customer s test boards and optimized process parameters from Part 1 and assess cleanliness level through visual inspection and ion chromatography Assess effect of cleaning agent on sensitive materials

71 Customer C Part 1: Cleaning company test vehicle used Eight (8) boards were populated with chip capacitors 0402, 0603, 0805, SOT-23, 1206, 1210, 1812, 1825 Water-soluble paste and flux used

72 Part 1 Customer C Two (2) boards were cleaned at customer site using DI-water Returned to cleaning company for cleanliness assessment and ion chromatography Six (6) boards were returned to cleaning company for cleaning and cleanliness assessment

73 Customer C Results Part 1: Optimum batch cleaning parameters were developed Wash Stage Equipment Cleaning Agent Concentration 10% Wash Time Batch Cleaner ph neutral micro phase 15 min Wash Temperature 140 F / 60 C Rinsing Agent Rinse Temperature Number Rinses Required Drying Method Drying Temperature Drying Time Rinsing Stage DI-water Drying Stage Room Temperature 5 each with a dwell time of 20 seconds Hot Circulated Air 150 F / 65.5 C 15 min

74 Customer C Results Part 1: Visual Inspection DI-water Cleaned ph neutral Cleaned Surface Inspection White residues remained Fully cleaned Undercomponent Inspection Residues remained Fully cleaned

75 Customer C Results Part 1: Visual Inspection Cleaned with DI-water Underneath 1825 Component Cleaned with ph neutral Underneath 1825 Component

76 Customer C Results Part 1: Visual Inspection Cleaned with DI-water Underneath 1812 Component Cleaned with ph neutral Underneath 1812 Component

77 Customer C Results Part 1: Visual Inspection Cleaned with DI-water Underneath 0402 Component Cleaned with ph neutral Underneath 0402 Component

78 Customer C Results Part 1: Visual Inspection Cleaned with DI-water Underneath 0603 Component Cleaned with ph neutral Underneath 0603 Component

79 Customer C Results Part 1: Ion Chromatography Anion Species Always Tested For (µg/in 2 ) Ionic Species Maximum Contamination DI-water Cleaned ph neutral Cleaned Limits Fluoride (F - ) Acetate (C 2 H 3 O 2- ) Formate (CHO 2- ) 3 ND ND Chloride (Cl - ) Nitrite (NO 2- ) 3 ND ND Bromide (Br - ) Nitrate (NO 3- ) Phosphate (PO 2-4 ) Sulfate (SO 2-4 ) WOA (Weak Organic Acid) 25 ND ND ND: Not Detected 0: Blank Value is higher than sample value

80 Customer C Results Part 1: Ion Chromatography Cation Species Always Tested For (µg/in 2 ) Lithium (Li + ) Sodium (Na + ) Ammonium (NH 4+ ) Potassium (K + ) Magnesium (Mg 2+ ) Calcium (Ca 2+ ) ND: Not Detected 0: Blank Value is higher than sample value

81 Customer C Results Ion Chromatography Both boards passed Ionic contamination present on board cleaned with ph neutral was less than what was present on the DI-water cleaned board Untouched flux residue remained under several components cleaned with DI-water

82 Customer C Results Part 2: Customer test boards utilized Four (4) used for under component assessment One (1) used for ion chromatography

83 Customer C Utilized batch cleaner and process parameters defined in Part 1 Boards were double-sided Wash temperature was increased to 150 F (previously using 140 F)

84 Customer C Results Part 2: Visual Inspection Cleaning Results Underneath Board # 101 Board # 102 Board # 103 Board # 104 C C C C C C C C R C C : Cleaned -: Uncleaned

85 Customer C Results Part 2: Visual Inspection Cleaning Results Underneath Board # 101 Board # 102 Board # 103 Board # 104 C C C C C C C C R C C C C C : Cleaned -: Uncleaned

86 Customer C Results Part 2: Visual Inspection Underneath C30 Component Underneath C82 Component Minor white residue in depth area

87 Customer C Results Part 2: Visual Inspection Underneath R50 Component Underneath C108 Component

88 Customer C Results Part 2: Visual Inspection Underneath C249 Component Underneath C227 Component

89 Customer C Results Part 2: Visual Inspection Underneath C200 Component Underneath C152 Component

90 Customer C Results Part 2: Ion Chromatography Ionic Species Anion Species Always Tested For (µg/in 2 ) Maximum Contamination Board # 105 Limits Fluoride (F - ) Acetate (C 2 H 3 O 2- ) 3 ND Formate (CHO 2- ) 3 ND Chloride (Cl - ) Nitrite (NO 2- ) 3 ND Bromide (Br - ) Nitrate (NO 3- ) Phosphate (PO 2-4 ) 3 ND Sulfate (SO 2-4 ) 3 ND WOA (Weak Organic Acid) 25 ND ND: Not Detected 0: Blank Value is higher than sample value

91 Customer C Results Part 2: Ion Chromatography Cation Species Always Tested For (µg/in 2 ) Lithium (Li + ) 3 ND Sodium (Na + ) 3 0 Ammonium (NH 4+ ) 3 0 Potassium (K + ) 3 0 Magnesium (Mg 2+ ) 1 ND Calcium (Ca 2+ ) 1 ND ND: Not Detected 0: Blank Value is higher than sample value